Well, this was Medieval I, so I don't recall any chariots present in that game, but you could dismount regular cavalry. Though, as Ludens said, you were limited by the battle type and only during deployment.
If Empire ever had enough modding tools to change the era, then you could have a mod with the dismounting of cavalry during the actual battle, but I'm not sure if the dismounted cavalry can move around when they are dismounted. I don't remember exactly how dragoons work in that game.
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